Knowledge of radical initiated grafting was summarized in theoretical part. It also contains a part about adamantane, its derivatives and a study of their use in polymer chemistry. In experimental part radical grafted polypropylene was prepared in batch mixer Brabender at 185 and 195 °C, 40 RPM and reaction time 5 min. Initiator 2,5-dimethyl-2,5-bis(tert-buthylperoxy)hexane (Trigonox 101) in concentrations between 0,2 – 4 wt % was used. 1-vinyladamantane was chosen as a monomer and its concetration ranged from 0,75 to 2,24 wt %. Mechanical properties of prepared samples were tested. Sample with content of initiator 0,2 wt % and monomer 1,4 wt % showed increase in notch toughness by 56,3 %, strength by 8,7 %, ductility by 11,5 % and decrease in MFR (230 °C; 2,16 kg) by 29,7 %. Values of torque indicated grafting reactions which couldn’t be proven by use of FTIR method so more suitable methods have been proposed.

Graphen, eine zweidimensionale Kohlenstoffstruktur, ist ein junger Füllstoff im Nanometerbereich und besitzt ausgezeichnete physikalische Eigenschaften. Da typische Füllstoffe im Mikrometerbereich, wie z. B. Glasfasern oder Ruße, an ihre Grenzen stoßen, werden zunehmend Nanofüllstoffe in polymeren Kompositen eingesetzt. Grund dafür ist ihre große spezifische Oberfläche und die daraus resultierenden Polymer-Füllstoff-Wechselwirkungen. Das große Potential von graphenbasierten Kompositen wurde bereits in vielen Studien nachgewiesen. Diese erfolgten jedoch vielmals im Labormaßstab und es existieren keine bekannten skalierbaren Prozesse zur Herstellung und Weiterverarbeitung dieser Materialien. Aus diesem Grund wurde in dieser Studie die gesamte Prozesskette von der Materialherstellung über die Verarbeitung bis zum Endprodukt im industriellen Maßstab berücksichtigt. Die Untersuchungen zeigen, dass die handelsüblichen Graphen-Typen keinem idealen Graphen entsprechen, da sie eine mehrschichtige und somit graphitartige Struktur aufweisen. Aufgrund der geringen Bindungskräfte zwischen den einzelnen Graphenschichten bilden die Agglomerate des Graphens eher eine Schwachstelle im Bauteil, so dass keine überproportionale Erhöhung der mechanischen Eigenschaften zu beobachten ist. Die elektrischen und thermischen Eigenschaften der graphenbasierten Verbindungen bleiben weit unter den Erwartungen. Das Forschungsprojekt zeigt die Möglichkeiten und Grenzen von graphenbasierten Kompositen. Derzeit ist mit den aktuell verfügbaren kommerziellen Graphen-Typen eine signifikante Verbesserung der Eigenschaften nicht zu erreichen. Daher ist die Übertragung der Ergebnisse aus Experimenten im Labormaßstab hin zu industriellen Anwendungen derzeit nicht möglich.

Coherent plane-wave compounding (CPWC) ultrasound is an important modality enabling ultrafast biomedical imaging. To perform CWPC image reconstruction for a stratified (horizontally layered) medium, one needs to know how the speed of sound (SOS) varies with the propagation depth. Incorrect sound speed and layer thickness assumptions can cause focusing errors, degraded spatial resolution and significant geometrical distortions resulting in poor image reconstruction. We aim to determine the speed of sound and thickness values for each horizontal layer to accurately locate the recorded reflection events to their true locations within the medium. Our CPWC image reconstruction process is based on phase-shift migration (PSM) that requires the user to specify the speed of sound and thickness of each layer in advance. Prior to performing phase-shift migration (one layer at a time, starting from the surface), we first estimate the speed of sound values of a given layer using a cosine similarity metric, based on the data obtained by a multi-element transducer array for two different plane-wave emission angles. Then, we use our speed estimate to identify the layer thickness via end-of-layer boundary detection. A low-cost alternative that obtains reconstructed images with fewer phase shifts (i.e., fewer complex multiplications) using a spectral energy threshold is also proposed in this thesis. Our evaluation results, based on the CPWC imaging simulation of a three-layer medium, show that our sound speed and layer thickness estimates are within 4% of their true values (i.e., those used to generate simulated data). We have also confirmed the accuracy of our speed and layer thickness estimation separately, using two experimental datasets representing two special cases. For speed estimation, we used a CPWC imaging dataset for a constant-speed (i.e., single-layer) medium, yielding estimates within 1% of their true values. For layer thickness estimation, we used a monostatic (i.e., single-element) synthetic-aperture (SA) imaging dataset of the three-layer medium, also yielding estimates within 1% of their true values. Our evaluation results for the low-cost alternative showed a 93% reduction in complex multiplications for the three-layer CPWC imaging dataset and 76% for the three-layer monostatic SA imaging dataset, producing images nearly similar to those obtained using the original PSM methods. / Graduate

Ce travail est développé dans le but d’élaborer, caractériser et mettre en œuvre de matériaux polymères à base de polysemicarbazides et polyesters furaniques bio-sourcés. L’étude comporte trois grandes parties : la synthèse et l’optimisation du procédé de synthèse de poly(acylsemicarbazide)s, la préparation de quelques mélanges de polymères en mini-bivis de polymères furaniques (PEF ou PSC) avec le PET, le PLA et le PHA et l’élaboration de nouveaux copolyesters furano-aliphatiques par polymérisation par ouverture de cycle (PEF/PCL) ou par réactions d’interéchanges à l’état fondu de mélange d’homopolymères (PEF/PCL, PEF/PLA et PEF/PHA). Nous rapportons dans le premier chapitre de ce mémoire la synthèse d’une série de dihydrazides bifuraniques et l’étude de leur réactivité vis-à-vis de divers diisocyanates aromatiques afin d’élaborer des polyacylsemicarbazides furano-aromatiques. Notre étude est abordée en examinant le comportement d’un système de monomères modèle dans différentes conditions expérimentales afin d’optimiser le procédé de polycondensation avant de l’appliquer à diverses combinaisons de monomères. Nous traitons dans le deuxième chapitre l’élaboration de nouveaux matériaux à base de polymères furaniques (PEF ou PSC) par mélange de polyesters à l’état fondu. Pour cela, nous avons élaboré 3 types de mélanges polyester furaniques / polyesters aliphatiques et aromatiques. Enfin, nous nous intéressons dans le troisième chapitre à la synthèse de divers polyesters furaniques à extrémités contrôlées : PEF-dihydroxy (PEF di-OH), PEF-dicarboxylé (PEF di-COOH), PEF-diéthylester (PEF di-COOEt) et PEF à extrémités mixtes (PEF di-OH/COOEt). Ces derniers ont été utilisés pour l’élaboration de nouveaux polyesters furano-aliphatiques par la technique de polymérisation par ouverture de cycle (PEF /PCL) ou suite à des réactions d’interéchange à l’état fondu à partir de mélanges d’homopolymères (PEF/PLA, PEF/PHA et PEF/PCL). / This work aims at elaborating, characterising and processing polymer materials based on bio-sourced polysemicarbazides and furanic polyesters. The study has three main parts : Synthesis and optimisation of the synthesis of poly(acylsemicarbazide)s, elaboration of polymer blends based on furanic polymers (PEF or PSC) with PET, PLA and PHA and elaboration of new furano-aliphatic copolyesters by ring opening polymerisation (PEF/PCL) or by inter-exchange reactions between ’homopolymers (PEF/PCL, PEF/PLA et PEF/PHA) in the melt. The first chapter reports on the synthesis of a serie of bifuranic dihydrazides and on the study of their reactivity with several aromatic diisocyanates in order to elaborate furano-aromatic polyacylsemicarbazides. The behaviour of model monomer systems in various experimental conditions is studied in order to d’optimise the polycondensation processbefore transfering it to several monomer combinations. In the second chapter, we study the elaboration of new materials based on furanic polymers (PEF or PSC) blended with polyesters in the melt. 3 kinds of blends based on furanic polyesters / aliphatic and aromatic polyesters. The third chapter is devoted to the synthesis of furanic polyesters with controlled ends : dihydroxy-PEF (PEF di-OH), dicarboxylate-PEF (PEF di-COOH), diethylester-PEF (PEF di-COOEt) as well as PEF with mixed ends (PEF di-OH/COOEt). The latest have been used for the elaboration of new furano-aliphatic polyesters by ring opening polymerisation (PEF /PCL) or after interexchange reaction in melt homoplymer blends (PEF/PLA, PEF/PHA and PEF/PCL).

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Polyethylene Terephthalate (PET) is one of the most important polymers in use today for packaging due to its outstanding properties. The usage of PET has grown at the highest rate compared with other plastic packaging over the last 20 years, and it is anticipated that the increase in global demand will be around 6% in the 2010 ¿ 2015 period. The rheological behaviour, thermal properties, tensile modulus, permeability properties and degradation phenomena of PET/clay nanocomposites have been investigated in this project. An overall, important finding is that incorporation of nanoclays in PET gives rise to improvements in several key process and product parameters together ¿ processability/ reduced process energy, thermal properties, barrier properties and stiffness. The PET pellets have been compounded with carefully selected nanoclays (Somasif MAE, Somasif MTE and Cloisite 25A) via twin screw extrusion to produce PET/clay nanocomposites at various weight fractions of nanoclay (1, 3, 5, 20 wt.%). The nanoclays vary in the aspect ratio of the platelets, surfactant and/or gallery spacing so different effect are to be expected. The materials were carefully prepared prior to processing in terms of sufficient drying and re-crystallisation of the amorphous pellets as well as the use of dual motor feeders for feeding the materials to the extruder. The rheological properties of PET melts have been found to be enhanced by decreasing the viscosity of the PET i.e. increasing the ¿flowability¿ of the PET melt during the injection or/and extrusion processes. The apparent shear viscosity of PETNCs is show to be significantly lower than un-filled PET at high shear rates. The viscosity exhibits shear thinning behaviour which can be explained by two mechanisms which can occur simultaneously. The first mechanism proposed is that some polymer has entangled and few oriented molecular chain at rest and when applying high shear rates, the level of entanglements is reduced and the molecular chains tend to orient with the flow direction. The other mechanism is that the nanoparticles align with the flow direction at high shear rates. At low shear rate, the magnitudes of the shear viscosity are dependent on the nanoclay concentrations and processing shear rate. Increasing nanoclay concentration leads to increases in shear viscosity. The viscosity was observed to deviate from Newtonian behaviour and exhibited shear thinning at a 3 wt.% concentration. It is possible that the formation of aggregates of clay is responsible for an increase in shear viscosity. Reducing the shear viscosity has positive benefits for downstream manufacturers by reducing power consumption. It was observed that all ii three nanoclays used in this project act as nucleation agents for crystallisation by increasing the crystallisation temperature from the melt and decreasing the crystallisation temperature from the solid and increasing the crystallisation rate, while retaining the melt temperature and glass transition temperatures without significant change. This enhancement in the thermal properties leads to a decrease in the required cycle time for manufacturing processes thus potentially reducing operational costs and increasing production output. It was observed that the nanoclay significantly enhanced the barrier properties of the PET film by up to 50% this potentially allows new PET packaging applications for longer shelf lives or high gas pressures. PET final products require high stiffness whether for carbonated soft drinks or rough handling during distribution. The PET/Somasif nanocomposites exhibit an increase in the tensile modulus of PET nanocomposite films by up to 125% which can be attributed to many reasons including the good dispersion of these clays within the PET matrix as shown by TEM images as well as the good compatibility between the PET chains and the Somasif clays. The tensile test results for the PET/clay nanocomposites micro-moulded samples shows that the injection speed is crucial factor affecting the mechanical properties of polymer injection moulded products.

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No description available.

No / The purpose of this work was to explore NIR spectroscopy as a PAT tool to monitor the formation of ibuprofen and nicotinamide cocrystals during extrusion based solvent free continuous cocrystallization (SFCC). Drug and co-former were gravimetrically fed into a heated co-rotating twin screw extruder to form cocrystals. Real-time process monitoring was performed using a high temperature NIR probe in the extruder die to assess cocrystal content and subsequently compared to off-line powder X-ray diffraction measurements. The effect of processing variables, such as temperature and mixing intensity, on the extent of cocrystal formation was investigated. NIR spectroscopy was sensitive to cocrystal formation with the appearance of new peaks and peak shifts, particularly in the 4800-5200 cm(-1) wave-number region. PXRD confirmed an increased conversion of the mixture into cocrystal with increase in barrel temperature and screw mixing intensity. A decrease in screw rotation speed also provided improved cocrystal yield due to the material experiencing longer residence times within the process. A partial least squares analysis in this region of NIR spectrum correlated well with PXRD data, providing a best fit with cocrystal conversion when a limited range of process conditions were considered, for example a single set temperature. The study suggests that NIR spectroscopy could be used to monitor cocrystal purity on an industrial scale using this continuous, solvent-free process.

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